Use the phrase to politely interrupt or inform others you can't speak because you're busy on a call. Can we talk later? I'm on the phone right now.
Pro Tip 2/3
Cultural Norms
In many cultures, it's considered rude to be on the phone while interacting face-to-face with others. Sorry, let me step outside. I'm on the phone with my boss.
Pro Tip 3/3
Call Duration
The phrase doesn't specify how long you'll be on the phone, just that you are currently engaged. I can't help you at the moment; I've been on the phone for a while.